Method for imparting water- and oil-repellent properties to leather and leather so treated

ABSTRACT

A method for imparting water- and oil-repellent properties to leather is disclosed which uses as the treating composition a solution of A. A CONDENSATION PRODUCT FORMED BY (1) AN ALUMINUM ALCOHOLATE OF A LOWER MONOHYDROXY ALCOHOL HAVING A CARBON CHAIN LENGTH OF ONE TO FOUR CARBON ATOMS WITH (2) A PHOSPHORIC ACID MONOESTER OF A HIGHER FATTY ALCOHOL HAVING A CARBON CHAIN LENGTH OF 12 TO 20 CARBON ATOMS, AND B. A FLUORINATED COMPOUND COMPRISING LIPOPHILIC RADICALS HAVING A CARBON CHAIN LENGTH OF EIGHT TO 20 CARBON ATOMS, SELECTED FROM THE GROUP CONSISTING OF FLUOROCARBOXYLIC ACIDS AND ESTERS THEREOF, AND FLUOROALCOHOLS AND ESTERS, ETHERS AND ACETALS THEREOF IN AN INERT ORGANIC SOLVENT; THE SOLUTION IS APPLIED TO DRY LEATHER BY IMMERSION OR SPRAYING, AS WELL AS THE WATER- AND OIL-REPELLENT LEATHER SO PRODUCED.

United States Patent Plapper et a1.

[4 1 May 9, 1972 [54] METHOD FOR IMPARTING WATER- AND OIL-REPELLENT PROPERTIES TO LEATHER AND LEATHER SO TREATED [72] Inventors: Jurgen Plapper, DusseIdorf-l-lolthausen;

Friedrich Pieper, Langenfeld-Richrath, both of Germany Henkel 8: Cie Holthausen, Germany [22] Filed: June 18, I970 [21] Appl.No.: 47,593

[73] Assignee: Gmbl-I, Dusseldorf [30] Foreign Application Priority Data I June 27, 1969 Germany ..P 19 32 630.8

[52] U.S.CI ..117/142,252/8.57

[51] Int. Cl. ...B44d I/32, Cl4c 7/00 [58] Field ofSearch ..252/8.57; 117/142 [56] References Cited UNITED STATES PATENTS 3,106,478 10/1963 Heyden et al. ..117/142 X 3,019,133 l/l962 Heyden et a1... ..117/142 3,524.760 8/1970 Pinkerton ....1 17/142 X $527,742 9/1970 Pittman et al.. ....117/142 X 2.953.479 9/1960 Heyden et a1 ..l l7/l35.5

2,977,249 3/1961 I-leyden et a1 ..l 17/l35.5 3,471,518 10/1969 Hager ..252/8.57 X 3,409,647 11/1968 Pittman et al..., ..252/8.57 X 3,501,448 3/1970 Pittman et al ..l l7/142 X FOREIGN PATENTS OR APPLICATIONS 824,436 12/1959 Great Britain "252/857 Primary E.\'aminer-William D. Martin Assistant E.\'aminerHarry J. Gwinnell Artorne v-Hammond & Littell [57] ABSTRACT A method for imparting waterand oil-repellent properties to leather is disclosed which uses as the treating composition a solution of a. a condensation product formed by l an aluminum alcoholate of a lower monohydroxy alcohol having a carbon chain length ofone to four carbon atoms with (2) a phosphoric acid monoester ofa higher fatty alcohol having a carbon chain length of 12 to 20 carbon atoms, and

16 Claims, No Drawings METHOD FOR IMPAR'I'ING WATER- AND OIL- REPELLENT PROPERTIES TO LEATHER AND LEATHER SO TREATED THE PRIOR ART From German Pat. No. 1,061,478 the use of condensation products of alcoholates of multivalent metals and acid highermolecular organic derivatives of the phosphoric acids in organic solvents for the impregnation of leather is known. The impregnation imparts water-repellent characteristics to the leather, especially good water-repellent effects being achieved and the absorption of water of the impregnated leathers is also reduced to a greater or less extent. At greater concentrations, however, the leathers become increasingly hardened and of a darker coloration, while the water absorption and the dynamic water resistance are increased only slightly.

The use of so-called fluoro-chemicals for the leather impregnation is also known. Such fluoro-chemicals include saturated or unsaturated fluorocarboxylic acids and fluoroalcohols of chain lengths C,, to C, and their esters and derivative's, as well as polymerizable fluorine-containing compounds such as for instance acrylic or methacrylic esters of fluorinated higher alcohols or esters and ethers of allyl alcohol with fluorinated higher carboxylic acids or alcohols or acetals of unsaturated aldehydes with fluorinated alcohols, etc.

In the impregnation with the fluoro-chemicals in organic solution, water and oil repellent leathers are obtained which show good water-repellent and oil-repellent effects. The dynamic water resistance is no better, however, than in the leathers impregnated with phosphoric acid ester condensation products. It is true that increasing the concentration of the fluoro-ehemicals applied reduces the water absorption but the characteristics of the leather deteriorate increasingly at the same time. The leathers become harder and more speckled. Furthermore, at increasing concentrations the oil-repellent effect is increasingly reduced.

OBJECTS OF THE INVENTION It is the object of the invention to achieve a better full impregnation and better water characteristic, especially a better dynamic water resistance of the impregnated leather, without any deterioration in the general character of the leather through hardening, spotting or discoloration.

Another object of the present invention is the development of a process for imparting waterand oil-repellent properties to leather which comprises impregnating a dry leather with an inert organic solvent solution containing from 0.5 percent to 6 percent by weight of a mixture of (A) from about 10 percent to 95 percent by weight of the condensation product of an aluminum alcoholate of an alkanol having from one to four carbon atoms with a phosphoric acid monoester of an alkanol having from 12 to 20 carbon atoms in a molar ratio of from l:O.5 to l:l.5 and (B) from about percent to 90 percent by weight of a fluorinated lipophilic compound having from eight to 20 carbon atoms selected from the group consisting of higher saturated and unsaturated fluoro-carboxylic acids and their esters with lower alkanols and lower alkenols, higher saturated and unsaturated fluoroalcohols, their esters with lower alkanoic and lower alkenoic acids, their ethers with lower alkanols and lower alkenols and their acetals with lower alkanals and lower alkenals, drying said impregnated leather at temperatures from room temperature to about 70 C and recovering a leather having waterand oil-repellent properties.

A further object of the invention is the obtaining of an inert organic solvent solution for impregnating leather to impart waterand oil-repellent properties thereto which contains from 0.5 percent to about 50 percent by weight of a mixture of (A) from about percent to 95 percent by weight of the condensation products of an aluminum alcoholate of an alkanol having from one to four carbon atoms with a phosphoric acid monoester of an alkanol having from 12 to' carbon atoms in a molar ratio offrom 110.5 to l:l.5 and (B) from about 5 percent to percent by weight of a fluorinated lipophilic compound having from eight to 20 carbon atoms selected from the group consisting of higher saturated and unsaturated fluorocarboxylic acids and their esters with lower alkanols and lower alkenols, higher saturated and unsaturated fluoro-alcohols, their esters with lower alkanoic and lower alkenoic acids, their ethers with lower alkanols and lower alkenols and their acetals with lower alkanals and lower alkenals.

A yet further object of the invention is the production of a leather having waterand oil-repellent properties having a surface impregnation of from about 1 gm/m to about 14 gm/m of leather surface of a mixture of (A) from about 10 percent,

to percent by weight of the condensation product of an aluminum alcoholate of an alkanol having from one to four carbon atoms with a phosphoric acid monoester of an alkanol having from 12 to 20 carbon atoms in a molar ratio of from 1:0.5 to l:l.5 and (B) from about 5 percent to 90 percent by weight of a fluorinated lipophilic compound having from eight to 20 carbon atoms selected from the group consisting of higher saturated and unsaturated fluoro-carboxylic acids and their esters with lower alkanols and lower alkenols, higher saturated and unsaturated fluoro-alcohols, their esters with lower alkanoic and lower alkenoic acids, their ethers with lower alkanols and lower alkenols and their acetals with lower alkanals and lower alkenals.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION The present invention, therefore, provides a process for the impregnation of leather, comprising contacting the leather with an inert organic solvent solution having a content of:

A. A condensation product of an aluminum alcoholate of a lower mono-alcohol of chain length C to C, with a phosphoric acid monoester of a higher fatty alcohol of chain length C to C and B. A fluoro-carboxylic acid or an ester thereof, or a fluoroalcohol or an ester, ether or acetal thereof, which has a fluorinated lipophile residue having a chain length of C to C In a further aspect, the present invention provides a composition which comprises an'inert organic solvent solution of:

A. A condensation product of an aluminum alcoholate of a lower mono-alcohol of 1 chain lengths C, to C, with a phosphoric acid monoester of a higher fatty alcohol of chain lengths C to C and B. A fluoro-carboxylic acid or an ester thereof, or a fluoroalcohol or an ester, ether or. acetal thereof, which has a fluorinated lipophile residue having a chain length of C to C in an organic solvent.

It has now been found surprisingly that the combination of the components A and B which are known per se, prevents the disadvantages which are present when the two impregnating components are used separately. A better penetrating impregnation and a substantially better water resistant character of the impregnated leather is achieved, without any deterioration of the general character of the leather through hardening, spotting, discoloration etc. A further advantage is that the concentration of the active solutions applied can be substantially increased which allows further improvements, in respect of water and oil-repellent effects and of the water resistance of the impregnated leather to be achieved without substantial alteration of the character of the leather.

More particularly, and as a further aspect of the present invention, the invention comprises a leather having waterand oilrepellent properties having a surface impregnation of from about 1 gm/m to about 14 gm/m of leather surface of a mixture of (A) from about 10 percent to 95 percent by weight of the condensation product of an aluminum alcoholate of an alkanol having from one to four carbon atoms with a phosphoric acid monoester of an alkanol having from 12 to 20 carbon atoms in a molar ratio of from l:0.5'to l:l.5 and (B) from about 5 percent to 90 percent by weight of a fluorinated lipoby weight, related to the sum of components A and B. After philic compound having from eight to 20 carbon atoms impregnating, the leather contains from about I gm/m to [4 selected from the group consisting of higher saturated and ungm/m of leather surface of themixture of components A and saturated fluoro-carboxylic acids and their esters with lower B. Possible inert organic solvents and diluents are chiefly alkanols and lower alkenols, higher saturated and unsaturated 5 gasolines of boiling ranges between -60 and 200 C, ethyl fluoro-alcohols, their esters with lower alkanoic and lower alacetate, butyl acetate, chlorohydrocarbons such as methylene kenoic acids, their ethers with lower alkanols and lower alv Chloride. m hy chloroform, h hy n P kenols and their acetals with loweralkanals and lower alhl r hy n l and pr ly mixture f kenals. gasolines of a boiling range of 60 to 95 C and ethyl acetate.

The condensation products of component A are obtained Th tr at nt O th l ath r m y be t by i s according to Gennan Pat. No. 1,061,478 by the reaction of but m inly howev r by praying nto he surface f the aluminum alcoholates, such as aluminum isopropylate or buleather. The leathers "eatcd pp p y in a dry tylate with phosphoric acid monoesters of higher fatty alt n- After p g a on. n f rrying at to 70 C.

cohols with 12 to carbon atoms. The reaction is effected by bringing together the starting components in olution in an r- 15 whereupon optimum water resistance is achieved immediateganic solvent such as isopropanol, trichloroethylene or ly. Favorable effects can also be achieved by after-drying at toluene and heating, if necessary, to temperatures of from room temperature, but this method requires a storing period about 30 to 50 C. The. molar ratio of alcoholate to phosphorof a few days.

ic acid ester should be approximately 1:0.5 to 1.5. Up to 30 2o Specially suitable for the impregnation in accordance with mol percent of phosphoric acid monoester may be replaced by the invention are types of suede leather such as shoe and the corresponding phosphoric acid diester of higher fatty alclothing suedes, but also non-finished or slightly finished types cohols. Suitable products of component A are the reaction of leather, such as the so-called aniline leathers.

product of 1 mol of aluminum isopropylate with 0.7 mols of a The combinations of active components may contain monoalkyl phosphoric acid ester with an alkyl having 12 to 18 furthermore the usual additives such as waxes, resins or dyes, carbon atoms, the reaction product of 1 mol of aluminum so as to obtain a favorable effect on the leather character in propylate with 0.9 mols of monotetradecyl phosphoric acid accordance with the different types of leather. For a further ester, the reaction product of 1 mol of aluminum butylate with increase of the water resistance commercial silicone oils on 0.6 mols of a monoalkylphosphate acid ester with an alkyl the basis of dimethyl polysiloxanes or methyl hydrogen having 16 to 18 carbon atoms. For stabilization before use polysiloxanes may be added to the impregnating solvent mixagainst the effects of moisture, compounds containing enol ture in amounts of from about 0.03 to 0.4 percent by weight.

groups, such as acetyl acetone and ethyl'acetoacetate, may be The following examples are illustrative of the practice of the added to the solutions of these products. invention without being deemedlimitative in any respect.

The compoundsof component B contains as a common characteristic a lipophile fluorinated hydrocarbon residue of EXAMPLES chain lengths C to C The compounds c n r are known Stock solutions are prepared of an aluminum aleoholate compounds from the P of the i saturaned unsam' phosphoric acid ester condensation product (solution A) rated fluoro-carboxylic acids or'their esters with lower satuand a mixture offlurorinated compounds (Solution from ester. it mixture of the methacrylic acid 'esters of per-.

rated or unsaturated alcohols preferably allyl alcohol as well which by mixing and further dilution the impregnating soluas from the group of the higher saturated or unsaturated or 40 tions ofthe following examples arebbtained.

branch-chained fluoro-alcohols and their esters, ethers or Solution A :rligggagg gl z nztfig gig gsgzgg: z sgg V 216 parts by weight of aluminum isopropylate aredissolved pounds of component B perfluorodecane carboxylic acid a v m 240 i gi r g i q fi g at tem- Y perature an com me gra ual y wit eat ng to 65 to 70 C m g of izi gzi i zg f i i gzgi and stirring with a solution of 200 parts by weight of a monoalp y y P kyl phosphoric acid ester mixture of chain lengths C to C in tluorododccyl alcohol, perfluorododecyl alcohol acrylic acid 200 pans by weight of perchloroethylene. To the clear Solu tion of the reaction mixture are added 144 parts by weight of ethyl acetate with stirring and the mixture is stirred for a further 2 hours at approximately 70 C. The solution contains fluorinated fatty alcohols of chain lengths C to C perfluorododecanol formaldehyde ucctal. In as far as the aforementioned com ounds are esters of acr lie or methacrylic acid, or esters o iethers of allyl alcohol, i he compounds are fi g X3 parts by of the aluminum alcoholate' able to polymerize and may also be used in the form of their g sg gg ac] ester condensation product soluble polymers of copolymers' '4.5 parts by weight of a mixture of approximately 1 part by The proportion of fluorinated compounds in the mixture of active components may be from 5 percent to 90 percent, preferably 10 percent to 50 percent by weight. Favorable effects can be achieved already with relatively small proportions of fluoro-compounds, so that the claimed process is partieuweight of perfluoroctane carboxylic acid and approximately 2 parts by weight of the methacrylic acid ester of a fluorinated unsaturated fatty alcohol mixture of average chain length C are dissolved in methyl chloroform.

larly advantageous also from an economic point of view. EXAMPLE 1 The products are applied in accordance with the present invention, in organic solution in concentrations of approximate- T0 32 parts by weight of solution A are added 40 parts by ly 0.5 to 6 percent by weight, preferably 1 percent to 4 percent Weight of solution B. The yellow, clear impregnating agent sol- Concentra- Penctrometer Percent water absorption tion applied, Test' Water according to Kubelka related to Drip test penetration. afterztctivc sub- Average from stance, percent Water Machine oil 3 tests 30 min. 2 hrs. 24 hrs. Characterization of the leather 1 40 minutes. 40 minutes 12 minutes. 46. 1 59. 8 80.3 Good handle. EXHIIIDIO 1 4 1 hour- 24 hours. 25 minutes 42. 8 54. 7 7i). 1 slightlty more greasy than with 1% active subs once. 1 1 hour. 24 hours..- 6 ininutcs 58. 1 70. 9 87. 1 Leather somewhat liardor. Solution B -t 30 minutes Ni) ctiicctat 12 niinutes- 46.!) (50.1 2.3 Leather hard and unattractive, spotted.

' iig i conconti' l)lniqthylsil-iixmiv 4 1 lioiir 7 minutes... (it). 2 72. 3 93.1 N 0 change against untreated. SO U -t d0 12 ininiitcs 56. 0 6-1.1 81 7 After bulfing, tendency to grcasincss.

Leather becomes coarser and harder. Uiitrvnlvd lvathrr 4 minutes 2 iiii iutes 115, 4 110. 0 131, 0 Character of aniline leather.

nun-u n 1 possibly in the presence of atmospheric moisture takes place.

vent mixture is diluted with further 21 parts by weight of a gasoline of boiling range 1 to 140 C and 7 parts by weight of butyl acetate. The approximately percent solution of active substance produced is further diluted before the application to the leather with a gasoline of boiling range 60 to 95 C or ethyl acetate to give a content of active substances of 1 percent and 4 percent by weight respectively.

A commercial, lightly retanned and dubbed chrome neats upper leather of the so-called aniline leather type is sprayed with 1 percent and 4 percent respectively active substance solution of the above-mentioned impregnating agent, so that in the first case approximately 2.5 gm/m of leather surface, and in the second case approximately 9 gm/m of leather surface are applied. After drying and maturing of the leather, the impregnating data given in the following table were obtained. The table also contains data which was obtained with solution A and with solution B respectively after appropriate dilution and with a dimethylpolysiloxane solution of appropriate concentration and with untreated leather.

The result clearly indicates that with the impregnating agents in accordance with the invention, without detrimental changes in the character of the leather, substantially better impregnating effects were obtained than with the individual components or with commercial dimethyl-polysiloxane.

EXAMPLE 2 To 28 parts by weight of solution A are added 36 parts by weight of solution B and 4 parts by weight of a commercial A commercial, lightly retanned and dubbed chrome neats upper leather of the aniline leather type, is treated as described in Example 1, with the above-mentioned impregnating agent and finished. The impregnating data are to be found in the following table. In spite of the relatively small quantity offluoro-compounds in the impregnating agent mixture a total effect much superior to that of the individual components is achieved.

EXAMPLE 3 To parts by weight of solution A are added parts by weight of solution B and the mixture is diluted with 10 parts by weight of butyl acetate. The yellow clear impregnating solu tion contains a proportion of active substance of approximately 15 percent by weight.

Concentration applied, related to active substance, percent Dii'p test \Vater Machine oil 3 tests 1 1 hour 10 minutes.

(1 24 hours.

Example 3 bolntlon It. too high coiicentr. l llnelli\'lsilo\:nn- -l Penetroinetcr Test: Water penetration. Average front 5 minutes. 54 minutes 24 hours 6 minutes. No effect at 12 minutes...

.. 7 minutes"... 1 1;. ininlitcs 2 iiiiiiiites Percent water absorption according to Kiibelka 30 min. 2 hrs. 24 hrs. Characterization of the leather No change against untreated. No change. Leather somewhat harder. I Lcathor hard and unattractive, spotted.

148. I No change against untreated. 7

I31. 0 Alter Inilling, tendency to lll'flllSllH-SS.

Leather rougher and harder.

M84 Leather velvety rlry.

EXAMPLE 4. To 28 parts by weight of solution A are added 36 parts by weight of solution B and 4 parts by weight of dimethylpolysiloxane, 28 parts by weight of butylacetate and 4 parts by weight of perchloroethylene while heating slightly. A yellow clear impregnating solution with a content of active substance of approximately 17 percent by weight is obtained.

Conccntra- Penetronieter Percent water absorption tion applied, Test: Water according to Kuhclka related to Drip test penetration. aftcr active suh- Average from I I stain-e, percent Water Machine oil 3 tests 30 min. 2 hrs. 24 hrs. Characterization of the. leather 1 1 1 hour- 5 minutes. 3 minutes..." 101. 5 107. 8 116. 0 No change to untreated. Exampl 4 4 do 24 hours minutes 32. o 56.1 85. 0 D0.

1 1 hour- 24 hours..- 6 minutes 107. 8 122. 8 132.0 Leather somewhat harder. 4 30 minutes. No efiect at 12 minutes-.. 65. 2 80.0 100. 5 Leather hard and unattractive, spotted. Solution 13 too high concentr. 4 Diinctliy1si1oxane. 4 1 hour 7 minutes 126. 8 140, 3 148.1 No change to untreated. Solution A 4 do 12 minutes 91, 7 122. 9 134. 0 After barring, tendency to greasiness.

Leather coarser and harder. Untreated leather 4 minutes 2 minutcs 137. 5 142.1 148, 4 Leather velvet like, dry.

A commercial clothing suede is sprayed as in Example 1 stance of approximately 1 percent and 4 percent by weight with an active substance solution of the above-mentioned imrespectively.

Concentra- Penetrometer Percent water absorption tion applied, I Test: Water according to Kubelka related to Drip test penetration. r active snb- Average from stance, percent Water Machine oil 3 tests 30 min. 2 hrs. 24 hrs. Characterization of the leather 1 1 hour- 25 minutes 5 minutes. 55. 5 68. 5 88.1 Good handle. Example 2 4 do 24 hours 15 minntes 53. 4 e4. 0 s1. 9 sllglgiitl; more greasy than with 1% active an s ance. 1 1 hour- 24 hours... 6 minutes 58.1 70. 9 87. 1 Leather somewhat harder. 4 30 minutes" No eflect at 12 minutes. 46. 9 60.1 82. 3 Leather hard and unattractive, spotted. bolution B 1. too high coneentr. Dimethyl siloxane. 4 1 hour 7 minutes 60. 2 72, 3 .13. 1 No change against untreated. Solution A 4 do 1 12 'minutcs 5s, 0 64.1 81. 7 After bulling tendency to grcaslnos Leather becornps rougher and harder. Untreated leather 4 minutes 2 minutes 115. 4 119. o 131. 0 Character of aniline leather.

pregnating agent adjusted to 1 -to-4 percent by weight.

After drying and maturing of the leather, an impregnating efiect was obtained which was superior compared with that of v the individual components, without any deterioration of the character of the leather.

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that the same is not limitative and that other expedients known to those skilled in the art may be practiced without departing from the spirit of the invention or the scope of the appended claims.

We claim:

l. A process for imparting waterand oil-repellent properties to leather which comprises impregnating a dry leather with an inert organic solvent solution containing from 0.5 percent to 6 percent by weight of a mixture of (A) from about 10 percentto 95 percent by weight of the condensation product of an aluminum alcoholate of an alkanol having from one to four carbon atoms with a phosphoric acid monoester of an alkanol having from 12 to 20 carbon atoms in a molar ratio of from 1:0.5 to l:l.5and B) fromaboutS percent to'90 percent by weight of a fluorinated lipophilic compound having from eight to, 20 carbon atoms selected from the group consisting of higher saturatedand unsaturated fluoro-carboxylic acids and their esters with lower alkanols and lower alkenols, higher saturated and unsaturatedfluoro-alcohols, their esters with lower alkanoic and lower alkenoic acids, their ethers with lower alkanols and lower alkenols and their acetals with lower alkanals and lower alkenals, drying said impregnated leather at temperatures from room temperature to about 70 C and recovering a leather having waterand oil-repellent properties.

2. The process of claim 1 wherein said component A is a condensation product of aluminum isopropylate with from 0.7 to L mols of a monoalkyl phosphoric acid ester having from l2 to 18 carbon atoms in the alkyl.

3. The process of claim 1 wherein said component B is a mixture of perfluorooctane carboxylic acid acid and a methacrylic acid ester of a fluorinated unsaturated fatty alcohol having an average of 8 carbon atoms.

4. The process of claim 1 wherein said component A is present in an amount of from 50 to 90 percent by weight and said component B is present in an amount of from to 50 percent by weight in said mixture.

5. The process-of claim 1 wherein said inert organic solvent is selected from the group consisting of gasoline fractions having boiling ranges between 60 C and 200 C, ethyl acetate, butyl acetate, trichloroethylene and toluene.

6. The process of claim 1 wherein the concentration of said mixture in said solution is from i to 4 percent by weight.

7. The process of claim 1 wherein said organic solvent solution contains from 0.03 to 0.4 percent by weight of a polysiloxane selected from the group consisting of dimethylpolysiloxanes and methyl hydrogen polysiloxanes.

8. The process of claim 1 whereinsaid organic solvent solution contains a content of an enolic compound as a stabilizer against moisture.

9. The process of claim 8 wherein said enolic compound is present in an amount of 1.mol per mol of component A and is selected from the group consisting of acetyl acetone and ethyl acetoacetate.

10. An inert organic solvent solution for impregnating leather to impart waterand oil-repellent properties thereto.

which contains from 0.5 to about 50 percent by weightof a mixture of (A) from about 10 to 95 percent by weight of the condensation product of an aluminum alcoholate of an alkanol having from one to four carbon atoms with a phosphoric acid monoester of an alkanol having from 12 to 20 carbon atoms in a molar ratio of from 120.5 to. 1:15 and (B) from about 5 to 90 percent by weight of a fluorinated lipophilic compound having from eight to 20 carbon atoms selected from the group'consisting of higher saturated and unsaturated fluoro-carboxylic acids and their esters with lower alkanols and lower alkenols, higher saturated and unsaturated fluoroalcohols, their esters with lower alkanoic and lower alkenoic acids, their ethers with lower alkanols and lower alkenols and their acetals with lower alkanals and lower 'alkenals.

11. The inert organic solvent solution of claim 10 wherein said component A is a condensation product of aluminum isopropylate with from 0.7 to 1.5 mols of a monalkyl phosphoric acid ester having from 12 to '18 carbon atoms in the alkyl.

12. The inert organic solvent solution of claim v10 wherein said component B is a mixture of perfluorooctane carboxylic acid and a methacrylic acid ester of a fluorinated unsaturated fatty alcohol having an average of eight carbon atoms.

13. The inert organic solvent solution of claim 10 wherein said component A is present in an amount of from 50 to percent by weight and said component B is present in an' amount of from 10 to 50 percent by weight in said mixture.

14. The inert organic solvent solution of claim 10 wherein said inert organic solvent is selected from the group consisting of gasoline fractions having boiling ranges between 60 C and 200 C, ethyl acetate, butyl acetate, trichloroethylene and toluene.

15. The inert organic solvent solution of claim 10 wherein the concentration of said mixture in said solution is from i to 4 percent by weight.

16. A leather having waterand oil-repellent properties having a surface impregnation of from about 1 gm/m to about 14 gm/m of leather surface of a mixture of (A) from about 10 to percent byweight of the condensation product of an aluminum alcoholate of an alkanol having from one to four carbon atoms with a phosphoric acid monoester of an alkanol having from 12 to 20 carbon atoms in a molar ratio of from 1:05 to 1:15 and (B) from about 5 to 90 percent by weight of a fluorinated lipophilic compound having from eight to 20carbon atoms selected from the group consisting of highersaturated and unsaturated fluoro-carboxylic acids and their esters with lower alkanols and loweralkenols, higher saturated and unsaturated fluoro-alcohols, their esters with lower alkanoic and lower alkenoic acids, their ethers with lower alkanols and lower alkenols and their acetals with lower'alkanals and lower alkenals. 

2. The process of claim 1 wherein said component A is a condensation product of aluminum isopropylate with from 0.7 to 1.5 mols of a monoalkyl phosphoric acid ester having from 12 to 18 carbon atoms in the alkyl.
 3. The process of claim 1 wherein said component B is a mixture of perfluorooctane carboxylic acid acid and a methacrylic acid ester of a fluorinated unsaturated fatty alcohol having an average of 8 carbon atoms.
 4. The process of claim 1 wherein said component A is present in an amount of from 50 to 90 percent by weight and said component B is present in an amount of from 10 to 50 percent by weight in said mixture.
 5. The process of claim 1 wherein said inert organic solvent is selected from the group consisting of gasoline fractions having boiling ranges between 60* C and 200* C, ethyl acetate, butyl acetate, trichloroethylene and toluene.
 6. The process of claim 1 wherein the concentration of said mixture in said solution is from 1 to 4 percent by weight.
 7. The process of claim 1 wherein said organic solvent solution contains from 0.03 to 0.4 percent by weight of a polysiloxane selected from the group consisting of dimethylpolysiloxanes and methyl hydrogen polysiloxanes.
 8. The process of claim 1 wherein said organic solvent solution contains a content of an enolic compound as a stabilizer against moisture.
 9. The process of claim 8 wherein said enolic compound is present in an amount of 1 mol per mol of component A and is selected from the group consisting of acetyl acetone and ethyl acetoacetate.
 10. An inert organic solvent solution for impregnating leather to impart water- and oil-repellent properties thereto which contains from 0.5 to about 50 percent by weight of a mixture of (A) from about 10 to 95 percent by weight of the condensation product of an aluminum alcoholate of an alkanol having from one to four carbon atoms with a phosphoric acid monoester of an alkanol having from 12 to 20 carbon atoms in a molar ratio of from 1:0.5 to 1:1.5 and (B) from about 5 to 90 percent by weight of a fluorinated lipophilic compound having from eight to 20 carbon atoms selected from the group consisting of higher saturated and unsaturated fluoro-carboxylic acids and their esters with lower alkanols and lower alkenols, higher saturated and unsaturated fluoro-alcohols, their esters with lower alkanoic and lower alkenoic acids, their ethers with lower alkanols and lower alkenols and their acetals with lower alkanals and lower alkenals.
 11. The inert organic solvent solution of claim 10 wherein said component A is a condensation product of aluminum isopropylate with from 0.7 to 1.5 mols of a monalkyl phosphoric acid ester having from 12 to 18 carbon atoms in the alkyl.
 12. The inert organic solvent solution of claim 10 wherein said component B is a mixture of perfluorooctane carboxylic acid and a methacrylic acid ester of a fluorinated unsaturated fatty alcohol having an average of eight carbon atoms.
 13. The inert organic solvent solution of claim 10 wherein said component A is present in an amount of from 50 to 90 percent by weight and said component B is present in an amount of from 10 to 50 percent by weight in said mixture.
 14. The inert organic solvent solution of claim 10 wherein said inert organic solvent is selected from the group consisting of gasoline fractions having boiling ranges between 60* C and 200* C, ethyl acetate, butyl acetate, trichloroethylene and toluene.
 15. The inert organic solvent solution of claim 10 wherein the concentration of said mixture in said solution is from 1 to 4 percent by weight.
 16. A leather having water- and oil-repellent properties having a surface impregnation of from about 1 gm/m2 to about 14 gm/m2 of leather surface of a mixture of (A) from about 10 to 95 percent by weight of the condensation product of an aluminum alcoholate of an alkanol having from one to four carbon atoms with a phosphoric acid monoester of an alkanol having from 12 to 20 carbon atoms in a molar ratio of from 1:0.5 to 1:1.5 and (B) from about 5 to 90 percent by weight of a fluorinated lipophilic cOmpound having from eight to 20 carbon atoms selected from the group consisting of higher saturated and unsaturated fluoro-carboxylic acids and their esters with lower alkanols and lower alkenols, higher saturated and unsaturated fluoro-alcohols, their esters with lower alkanoic and lower alkenoic acids, their ethers with lower alkanols and lower alkenols and their acetals with lower alkanals and lower alkenals. 